Monoalkenyl-succinic acid mono-ester salts



Patented .Iui' 31,1945

UNITED .STAT-ES'H PAT T OFFICE uouoaummm-svcmmc acm mono-mm SAL'IB Lucas 1'.

Kyrldu. to Monsanto Chemical Webster Groves. I... adgnor m sticati n a corporation of Delaware No Drawing. Application March 2, 1M2, Serial No. 432,997

Claims. (Oi. zoo-4:5) v

action of mono-oleiins or alkyl halides with \mand are salts of partial esters or such alkenyl-substituted polycarboxylic acids. I

In my prior copending application, Serial Numher 181,597, filed December 24, 1937, which has issued as Patent 'Number 2,283,214, of which this application is a continuation-in-part, I have disclosed washing, wetting and emulsiiyins sents which are typified by a water-soluble alkali-metal salt 0! an alkenyl-substituted acid resultin from the condensation oi maleic-anhydride with triisobutylene, which acid is called triisobutenyl-succinic acid and may be represented by the iormula:

in which "AlkenyP represents the triiscbutylene residue. In said copending application I also disclosed salts oi. partial esters of such alkenyl-substituted acids which are useful as washing. wetting and emulsify n agents, for example, the

sodium 'salt of the mono-ethyl ester oi triisobutenyl-succinic acid, in which one oi the carboxyl groups has been esterifled by ethyl alcohol and in the other carboxyl group the hydrogen has been replaced by sodium, according to the following formula: 1

H [Alkenyl-(J-COO-lNa mc-coo-- can Theexactpositionoithesodiumandethyi group has not been determined, hence the bracketed formula is used to indicate-this uncertainty.

pplicatimSerialNumberlalfiimlidiscloeedn'iethodsotiormingalk owl-substituted acids by the summation or rethe present invention,

saturated carbomlic acids containing the alphaacids which are suitable for the condensation with Y mono-olefin! or dbl-halides are these represented'bytheiormula:

' a-c-coon inwhichnisselectediromthesroupconsistins of hydrogen. alkyl and carbonyl radicals. Specific examples oi such unsaturated carboxylio acids are or maleic acid; HOOGCH=CH--OOOE. itaconic acid, .CH:=C (COOK) -CHa-CO0H,

citraconic acid, GE's-C(COOH) ==CH-.COOH.

acrylic acid, CH:=CE-COOH. and crotonic acid, CH|-CH=CHCOOH, The alkenyl-substituted acidresultinzattcrtheeondensationoi suchaclds with a mono-olefin or an alkyl halide seneral formula w pending 480,683,1iled February 12, 1942, is directed specificaliy to the method 0! reacting alkyl halides with maleic anhydride and similar unsaturated carboxylic acids or anhydrides to obtain such alkenylsuhstituted acids and contains additional examples not present in the disclosure of the prior applica- .tion, SerialNumber 181,597. p

' The-present application is directed specifical y to salts or partial esters of such alkenyl-substituted acids which are polyoarboxylic, that is. contain two or more carboxyl groups. Accordingly, the compounds whose use as washing, wetting and emulsifying agents is contemplated by general formula:

- 12 Albany JJ-coox --'d--coo- Y beta-anal grouping. Such unsaturated earborylic hastheapplication, Serial number may be represented by the in which x is a metal that will provide a watersoluble salt, such as sodium or other alkali-metal,

Y is an alkyl group having less than 17 carbon atoms such as ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyL'tridecyl, tetradecyl, pentadecyl and hexadecyl radicals, or a radical or an etherifled glycol having one. free hydroxyl group such as that or the,

mono-ethyl ether of ethylene glycol (-CHz-O-Cr-Ht) I or a radical of an etheriiled glycerol having at least one free hydroxyl group such as that of the diethyl ether of glycerol I alkyl halide containing not less than live nor more'than sixteen carbon atoms.

A method oi making salts or the partial esters or alkenyl-substituted polycarboxylic acids which are contemplated?! the present invention comprises first forming the corresponding acid by the reaction of a mono-olefin such'as diisobutylene or triisobutylene or an alkyl halide such as do-' assumes I The unsaturated polycarboxylic acids containing the alphai-beta enal grouping which are used for the preparation correspond to the following general formula:

' in which a is .a hydrogen, alkyl or carboxyl radidecyl chloride with an unsaturated 'polycarboxylic acid'containing the alpha-beta-enal group- .ing according to the processes of my prior applications or as more fully disclosed herein. The alkenyl-substituted acid is then partialLv eaterifled and this ester is converted to a water-sol-v uble salt by neutralization with a metal hydroxide Y or. carbonate.

It is preferred; however, in preparing the'compounds of the invention, first to make the anhydride of the alkenyl-substituted fpolycarboxylic acid'by condensing the olefin with the anhydride of the unsaturated acid, and thereafter "to con- 'ot triisobutenyl-succinic acid:

and thereafter partially vert the alkenyl-substituted polycarboxylic, acid nhydride to the monoester and neutralize the product to obtain the desired salt or the monoester. This method. which is, i' course, only operative with those unsaturated acids that form anhydrides, is

The mmpohnah or the invention as also be made by condensing an ester or the unsaturated acid, such as'the dihexyl ester oi maleic acid with triisobutylene or other olefin or alkyl halide. hydrolysing or saponiiy-' ing the resulting dlester of the, alkenyl-substituted acid, for example, dihexyl ester or triisobutenyl-succinic acid, to obtain the acid or salt of the monoester of the methyl-substituted acid.

- a illustrated in Example 1 ,herein after.

cal. such acids are, tor example, fumaric or ic acid, 'HOOC-CH=CHCOOH,' citraconic acid, cm-c(coon)=on-coon, ethylene-tetracarboxylic acid.

(H) 2--C=C (CQUH) 2:

and the like, or more generally,

' ao-ooon in which the we have the foregoing significance but of which at least one is a carboin'rl group. Thus, itaconic acid,

which does' not coniorm-to the previous fformula, but which does undergo condensation with oleflns', gives an acid coniorming most probably to Formula]: below (which corresponds to the general formula of the-acids ,irom which the compounds of the'present invention are derived) rather than Formula 11 below:

' mn i cni on; em i i-coon in et-woe n ooon m 4160s I m coon E1 -ooonmnemonic roman-r Formulall The resulting alkene substituted polycarboxylic acids resulting from condensation oi the foregoing unsaturated polycarboxylic'aclds, will take their names irom the corresponding saturated acid. .Thus, the alkenyl-substituted acids resulting irom condensation with maleic acid or anhydride are alkenyl-succinic acids, whereas resulting from itaconi'c or citraconic acids are alkenyl-pyrotartaric acids (methylsuccinic acids),

It is notn in my compounds that the two carboiwl groups orthe unsaturated polycarbonlic acid or the alkenyl-substituted acid be present on adjacent carbon atoms, as shown in some of the above general formulae. These tormlilae are merely to be considered as exemplary ot'preierred species,'which include most of the common unsaturated polyc boxylic acids containing the alpha-beta-enal grouping and the alk'enyl -substituted polycarboxylic acids resulting therefrom by condensation. More generally, the salts of 1 w h esters whose use is contemplated according to the present invention. are those salts of esters of acids resulting from condensation or reaction of monooleflns or alkyl chlorides having from live to sixteen carbon atoms, inclusive, with unsaturated polycarboxylic acids'containing the alnha-beta-enal grouping. The allrenyl groups representd'hn the loregoing rormulae are those containing iromlive to sixteen carbon atoms, inclusive, within which Jrange compounds having the most desirable wet- -for example, sodium salt or the monohexyl ester This method is illustrated in Example 2..

ting, washing and emulsifying properties occur; Preferred alhenyl groups are those resulting irom polymerized oleilns such-as diisobutylene,

comparable in their surface activity triisobutylene and tetraisobutylene; and triisobutylene is a preferred species.

The salts of partial esters of alkenyl-substituted polycarboxylic acids described herein are to wellknown wetting agents and detergents such as the sulfated alcohols and the sulfonated alkyl aromatic hydrocarbons commonly used for this purpose, but many of them do not foam or lather as readily when added to water in the manner that is typical of other wetting agents and detergents. This failure to foam is a definite advantage for certain purposes, and does not detract from their, desirability as wetting agents or detergents. They compare favorably with the salts of unesterifled alkenyl -substituted carboxylic acids which are specifically claimed in my prior copending application, Serial Number 181,597, and exhibit somewhat faster wetting ac- 7 tion. Allienyl-substituted acids, whether monocarboxylic or polycarboxylic, such as described in my prior copending application, Serial Number 181,597 and herein, when completely esterifled so that a solubilizing unesterified carboxyl or metal-substituted carboxyl group, such as COONa, that is capable of yielding positive ions, is absent, lack both solubility and other properties which make for good wetting and detergent action. p

In the examples which follow the various alkenyl-substituted polycarboxylic acids or anhydrides of such acids which are specified may be made by the methods described in U. S. Patent No. 2,055,456, or as more particularly described in my prior applications, Serial Numbers 181,597 and-430,633. For the preparation of anhydrides of these alkenyl-substituted polycarboxylic acids the following procedures, exemplified by the preparation of diisobutenyl-succinic and triisobutenyl-succinic anhydrides, may be used:

tillation conditions reach a temperature of about 125 C. at a pressure of about 185 mm. of mercury. The pressure is then slowly decreased until a pressure of 2 mm.is reached. The distillation is then taken to a temperature of 140 C. at

2 mm. The triisobutenyl-succinic anhydride which remains as the residue may be used without additional purification or it may be purified by further. distillation at 'a higher vacuum, for example, a vacuum of the order of about 1 mm. The distilled product, having a boiling range of about 135 to 145 C. at a pressure of about 1 mm., which is obtained according to this preparation, amounts to about 545 grams, which is about 60% of the yield theoretically possible from the amount of reactants charged to the autoclave.

The distilled product obtained as above described had a neutralization equivalent of 132.1, as determined acidimetrically. -The molecular weight of triisobutenyl-succinic acid anhydride is 266, and its theoretical neutralization equivalent is therefore 133. The proportions of reactants used may be varied, as is obvious.

Preparation 2.DiisobutenyZ-succinic anhydride Into a rotating steel autoclave arecharged 392 grams (about 4.0 mols) of maleic anhydride and 750 grams (about 6.? mols) of diisobutylene, The autoclave is sealed and, while it is rotated, it is gradually heated to 207 C. (405 F.) during the course of about 1 hours and maintained at about that temperature for an additional period Of about 2% hours. The recovery of the product is made'by the general method of distillation in vacuum used in Preparation 1.

The boiling range of diisobutenyl-succinic anhydride is approximately 132 to 134 C. at a pressure of 1 mm. of mercury. The yield is about 608' grams of product, which is about 72% of that theoretically obtainable from the charge used. The neutralization equivalent of diisobutenyl-succinic acid anhydride that has been distilled within the range descriged is 103.0. The molecular weight of diisobute yl-succinic acid anhydride is 210 and the theoretical neutralization equivalent is therefore 105.

The washing, wetting and emulsifying agents of the invention, which consist. of water-soluble metal salts of partial esters of the alkenyl-substituted polycarboxylic acids, may be produced from the alkenyl-substituted polycarboxylic acids or anhydrides according to general procedures illustrated in the examples which follow:

Example 1.-Sodium salt of mono-n-amyl triisobutenyZ-succz'nate Into a flask/provided with a stirrer and thermometer arm charged 266 grams (about 1 mol) of triisobutenyl-succinic anhydride, prepared, for example, as described in Preparation 1 above, and 88 grams (about 1 mol) of n-amyl alcohol. The charge is heated with stirring to about 100 to 110 C. and maintained at that temperature for a period of about three hours. The resulting product is cooled, any insoluble oil which separates is discarded, and the product is then poured into a solution of 53 grams /2 mol) of anhydrous sodium carbonate (NazCOa) dissolved in 2 liters of water. The product may be recovered as a solid from the solution by drying on a drumdrier.

The foregoing procedure is adaptable generally to the production of all water-soluble metal salts of alkenyl-substituted polycarboxylic acid partial esters from the corresponding alkenylsubstituted polycarboxylic acid anhydrides by substituting the alcohol corresponding to the ester desired. Sodium hydroxide in equivalent amount (40 grams) may be substituted for the sodium carbonate. Potassium carbonate or hydroxide in equivalent amount may be substituted for the sodium carbonate when the potassium salts are the desired products,

Example 2.-Sodium salt of mono-n-butyl triisobutenyl-succinate' After drying, the solution is fractionated in a column to get an oil havinga boiling point'of about 170 to 185 C. at a pressure of 16 to 5 mm. 5

of mercury. The product is a pale yellow oil with green fluorescence and is the dibutyl ester of triisobutenyl-succinic acid.

The foregoing diester is saponlfied to give the sodium salt of the monobutyl ester of triisobutenyl-succinic acid by heating 39.6 grams (0.1 mol) of the diester with 4 grams (0.1 mol) of sodium hydroxide dissolved in 125 cc. of water and 30 cc. of ethyl alcohol under gentle reflux for several hours. ing is separated by filtration and the resulting filtrate is made neutral. The resulting salt is recovered by evaporation or other suitable method.

Aqueous solutions of the compounds specified in this invention and related compounds for comparison were prepared for the purpose of making Draves wetting tests according to the procedure outlined in the 1931 and 1932 yearbooks of the American Association of Textile Chemists and Colorists. These solutions were diluted with 'water to various concentrations (0.25% and 0.125%) and were tested for wetting 30 action by determining the time required for a cotton thread-consisting of a 5-gram skein of unbleached cotton made up of 70/2 cotton yarn (70 twists per inch 2-ply yarn folded so as to be immersed in the solution) to be completely im- 35 mersed in the solution contained in a tall cylinder. In making the test a l -gram sinker, which is itself attached to a heavier weight by means of 1 inch of fine thread, is tied to the center of the test threadand the time detero mined is that which is required for the test thread to sink under the weight of the l fiz-gram sinker. The heavier sinker is used so that the test thread iscompletely in contact with the solution at the startof' the test and the time 45 Concentration of solution Compound 5 0.25% 0.125% 3 Diimbutenyl-succinio acid derivatives:

odium salt of mono-n-butyl ester 12. 6 143. 6 Sodium salt of mono-2-ethylhexyl, ester. Inst. 26. 7 Sodium saltoi monolauryl (dodecyl) ester. 42. l 92. 9 'lriisobutenyl-suocinic acid derivatives:

Sodium salt (di) 9.0 50. Sodium salt of monoethyl ester 3. 4 7. 5 Sodium salt of monopropyl ester- 3.0 8.8 Sodium salt of mono-u-butyl ester... Inst. 6. 8 Sodium salt of mono-n-amyl ester. Inst. 30. 2 Sodium salt of mono-n-hexyl ester Inst. 61. 1' Sodium salt of mono-2-ethylhexyl ester 38.0 82. 9 Dodecenyl-succinic acid derivative: Sodium salt of mono-n-butyl ester 31 24. 7 Tetraisobutenyl-succinic acid derivatives:

Sodium salt of monoethyl ester Inst. 20. 2 .Sodium salt of mono-n-butyl ester 17.9 42. 2 Comparison compounds:

"Santomerse 12.9 34. 9 GardinoP' 16.0 so. 6 7

In the foregoing results it is to be observed that, in the series of sodium salts of the half esters of triisobutenyl-succinic acids, a maximum mono-n-butyl ester. v t:ompound of this series of sodium salts of polyisobutenylvsucoinic acid half-esters having a total carbon-atom content of about 16 to 24 car- Any unsaponified oil remainl5 The values in the body 50 approximately ethyl to hexyl (2 to 6 carbon atoms) and that the octyl has less wetting action than the disodium salt of the acid. In the series consisting of sodium salts of diisobutenyl-succinic acid half esters, the maximum wetting action appears at about the mono-n-octyl ester, while in the series of sodium salts of tetraisobutenyl-succinic acid half esters, the wetting action is at its peak below the sodium salt of the Thus, it is apparent that a icon atoms, inclusive (including those in the carboxyl groups), and preferably between 18 and 22 carbon atoms, gives the best wetting action.

STANDARD Son. Leunonaomnrnn Tss'rs Standard soil launderometer tests were made with the sodium salt of triisobutenyl-succinic acid and Santomerse, a commercial detergent consisting of a sodium salt of an alkylated aromatic sulfonic acid, for comparison. The standard soil washing test is conducted as follows: To a cotton fabric is applied under controlled conditions a. standard soil solution which is composed of carbon black, vegetable oils and mineral oils in water. The fabric is then aged for a predetermined period. The aging of thefabric is important because the soil is more difficult to remove as it becomes older. The soiled fabric is then washed in a launderometer with a, 0.20% aqueous solution of the test detergent and each sample is tested in triplicate at various washintervals (10, 20, 30 and 40 minutes). The washed sample is then dried and the lightening of the fabric is determined, using a Pulfrich photometer. The relative detergency is then established.

The table illustrates the improvement in whiteness expressed as per cent baryta white units" obtained with the detergents when used in both hard and soft water.

Improvement in whiteness (percent baryta white units) Stficiiulm Igall; l. 0 r1 so u- Santomersetenyl-succinic acid Soft water (50 ppm.):

1st Wash min.) 8 5 M 2nd Wash (20 min.).. 7 3rd wash 230 min.) 18 9 4th wash 40 min.) 21 l1 0 Hard waten (300 ppm.):

1st wash (10 miu.). 13 12 2nd wash min.) l7 18 3rd wash min I 18 21 4th wash min.) 20 24 In the following results with the compounds more specifically described in this application the values represent those obtained in the standard soil launderometer test conducted as above, and represent the ratios (in percentages) of soil removal with the test compound to soil removal obtained with Gardinolf a mixture of the sodium salts of sulfated alcohols consisting of alcohols having from approximately 10 to 16 carbon atoms in the molecule, predominantly those having an even number of carbon atoms.

,The per cent soil removal is determined by means of a Universalphotoelectric photometer instead The results tabulated assume 5 0.20% aqueous solutions of the compounds were used, as before, for the washings.

Relative detergency (W- cent Compound Soft water Hard water (60 pp (30 pp Diisobutenyl-succinic acid derivatives:

Sodium salt oi mono-n-butyl ester. 60 83 Sodium salt oi mono-Hthyllicxyl ester 91 84 Sodium salt of monolauryl (dodecyl) ester 118 48 Triisobutenyl-suocinic acid derivavos:

Sodium salt oi monoethyl ester... 67 110 Sodium salt of monopropyl ester 79 94 Sodium salt of mono-n-butyl ester. 86 77 Sodium salt of mono-n-omyl ester. 106 98 Sodium salt of mono-n-hexyl ester. i25 72 Sodium salt of mono-z-ethylhexyl ester 122 62 Dodecenyl-succinic acid derivative:

Sodium salt of mono-n-but lester. 92 85 T taitraisobutenyl-succinie sci derivaves:

Sodium salt oi monoethyl ester..- 112 64 Sodium salt of mono-n-butyl ester. 117 61 Com 11 compounds:

Santomerse" 100 100 Gardlnol I 100 100 2 The sodium salts of the half esters, as can be seen from the values above, are, in general, better detergents in soft water than in hard water, whereas the disodium salt of the unesterlfled alkenyl-succinic acid is better in hard water than in soft water. It is also to be noted that detergency of th salts of the half esters increases with the length of the ester chain in soft water but decreases in hard water.

The compounds of the invention are of value in the preparation of detergents, polishes, wax and hydrocarbon-oil emulsions, insecticidal emulsions, cold-water paints and as thickening agents for rubber latex, as flotation reagents, as pigment-treating agents to improve dispersibility and grinding properties, as rubber-compounding ingredients and the like. They are of especial value for the preparation of detergents, for which purpose they are equal to or superior to sulfonated detergents such as alkyl aromatic sulfonlc acids. The calcium salts of the compounds are soluble in water.

By the term wetting agen as used in the specification and claims is to be understood an agent suitable for use as a detergent, emulsifying agent, textile assistant, dispersing agent, etc.,

or, in general, agents whose properties of reducing surface tension of liquids make them eminently desirable for many applications dependent upon their surface activity.

To the acids and salts of the invention various adiuvants or builders may be added, for example,

such materials as sodium carbonate, sodium sulfate, magnesium sulfate, etc., particularly when the products are to be used as detergents.

Inasmuch as the abov specification comprises preferred embodiments of the invention it is to be understood that the invention is not limited thereto and that changes and modifications may be made therein without departing substantially from the invention, which is defined in the appended claims.

I claim:

1. The sodium salt of the mono-n-butyl ester of triisobutenyl-succinic acid.

2. An akali-metal salt of a mono-ester of a 5 mono-alkenyl-succinic acid and an aliphatic alcohol, said ester having a total carbon atom content in the range of 16 to 28, the alcohol radical of said mono-ester having from 2 to 14 carbon atoms, said alkenyl residue having at so least 8 carbon atoms.

radical of said mono-ester having from 2 to 14 carbon atoms, said polyisobutenyl residue having at least 8 carbon atoms.

4. An alkali-metal salt of a mono-ester of a mono-triisobutenyl-succinic acid and an allphatic alcohol, the alcohol residue of said monoester having from 2 to 12 carbon atoms.

5. An alkali-metal salt of a mono-ester of a mono-diisobutenyl-succinic acid and an aliphatic alcohol, the alcohol residue of said mono-ester 5 having from 4 to .14 carbon atoms.

LUCAS P. minus. 

